Field of the Invention
The present invention relates to reducing the sulfur content from a mixture of hydrocarbons and oxidized sulfur compounds formed by oxidative desulfurization.
Description of Related Art
The discharge into the atmosphere of sulfur compounds during processing and end-use of the petroleum products derived from sulfur-containing sour crude oil poses health and environmental problems. Stringent reduced-sulfur specifications applicable to transportation and other fuel products have impacted the refining industry, and it is necessary for refiners to make capital investments to greatly reduce the sulfur content in gas oils to 10 parts per million by weight (ppmw) or less. In the industrialized nations such as the United States, Japan and the countries of the European Union, refineries have already been required to produce environmentally clean transportation fuels. For instance, in 2007 the United States Environmental Protection Agency required the sulfur content of highway diesel fuel to be reduced by 97%, from 500 ppmw (low sulfur diesel) to 15 ppmw (ultra-low sulfur diesel). The European Union has enacted even more stringent standards, requiring diesel and gasoline fuels sold in 2009 to contain less than 10 ppmw of sulfur. Other countries are following in the footsteps of the United States and the European Union and are moving forward with regulations that will require refineries to produce transportation fuels with ultra-low sulfur levels.
To keep pace with recent trends toward production of ultra-low sulfur fuels, refiners must choose among the processes or crude oils that provide flexibility that ensures future specifications are met with minimum additional capital investment, in many instances by utilizing existing equipment. Conventional technologies such as hydrocracking and two-stage hydrotreating offer solutions to refiners for the production of clean transportation fuels. These technologies are available and can be applied as new grassroots production facilities are constructed. However, many existing hydroprocessing facilities, such as those using relatively low pressure hydrotreaters, represent a substantial prior investment and were constructed before these more stringent sulfur reduction requirements were enacted. It is very difficult to upgrade existing hydrotreating reactors in these facilities because of the comparatively more severe operational requirements (i.e., higher temperature and pressure) to obtain clean fuel production. Available retrofitting options for refiners include elevation of the hydrogen partial pressure by increasing the recycle gas quality, utilization of more active catalyst compositions, installation of improved reactor components to enhance liquid-solid contact, the increase of reactor volume, and the increase of the feedstock quality.
There are many hydrotreating units installed worldwide producing transportation fuels containing 500-3000 ppmw sulfur. These units were designed for, and are being operated at, relatively mild conditions (i.e., low hydrogen partial pressures of 30 kilograms per square centimeter for straight run gas oils boiling in the range of 180° C. to 370° C.).
With the increasing prevalence of more stringent environmental sulfur specifications in transportation fuels mentioned above, the maximum allowable sulfur levels are being reduced to no greater than 15 ppmw, and in some cases no greater than 10 ppmw. This ultra-low level of sulfur in the end product typically requires either construction of new high pressure hydrotreating units, or a substantial retrofitting of existing facilities, e.g., by incorporating gas purification systems, reengineering the internal configuration and components of reactors, and/or deployment of more active catalyst compositions.
Sulfur compounds can be classified into four groups according to their hydrodesulfurization reactivity described by the pseudo-first-order rate constants. See, e.g., X. Ma et al., Ind. Eng. Chem., 1994, 33, 218; X. Ma et al., Ind. Eng. Chem. Res., 1995, 34, 748. These groups are:
The first group is predominantly alkyl benzothiophenes (BTs); the second, dibenzothiophenes (DBTs) and alkyl DBTs without alkyl substituents at the 4- and 6-positions; the third group, alkyl DBTs with only one alkyl substituent at either the 4- or 6-position; the fourth group, alkyl DBTs with alkyl substituents at the 4- and 6-positions. The sulfur content in the four groups is 39, 20, 26 and 15 wt. %, respectively. The relative hydrodesulfurization rate constant for each of the four groups is 36, 8, 3, and 1, respectively.
When the total sulfur content is reduced to 500 ppmw, the main sulfur compounds remaining in the hydrotreated effluent are the third and fourth groups. When the total sulfur content is reduced to 30 ppmw, the sulfur compounds remaining are only the fourth group sulfur compounds, indicating that the lower sulfur content organosulfur compounds have lower hydrodesulfurization reactivity. See D. D. Whitehurst et al., Catalysis Today, 1998, 45, 299.
Consequently, these species from the third and fourth groups are referred to as refractory sulfur compounds. Both steric hindrance and electronic density factors contribute to the low reactivity levels of 4- and 6-substituted DBTs in hydrodesulfurization process. See X. Ma et al. (1995); M. Daage et al., J. Catal., 1994, 194, 414.
The economical removal of refractory sulfur-containing compounds is therefore exceedingly difficult to achieve, and accordingly removal of sulfur-containing compounds in hydrocarbon fuels to an ultra-low sulfur level is very costly by current techniques. When previous regulations permitted sulfur levels up to 500 ppmw, there was little need or incentive to desulfurize beyond the capabilities of conventional hydrodesulfurization, and hence the refractory sulfur-containing compounds were not targeted. However, in order to meet the more stringent sulfur specifications, these refractory sulfur-containing compounds must be substantially removed from hydrocarbon fuels streams.
Compared with conventional catalytic hydrodesulfurization, oxidative desulfurization (ODS) can be performed under mild conditions, i.e., relatively low temperature and under atmospheric pressure conditions. ODS typically uses an oxidizing agent, such as hydrogen peroxide, organic peroxide, peracid and ozone, in addition to an oxidation catalyst. In the oxidation process, the divalent sulfur atom of refractory sulfur compounds (condensed thiophene) is oxidized by the electrophilic addition reaction of oxygen atoms to form the hexavalent sulfur of sulfones. The chemical and physical properties of sulfones are significantly different from those of the hydrocarbons in fuel oil. Therefore, sulfones can be removed by conventional separation methods such as filtration, solvent extraction and adsorption. An effective ODS process which has been shown to decrease sulfur in transportation fuel from 1100 ppm to 40 ppmw, is described in Al-Shahrani et al. WO/2007/103440 and in Al-Shahrani et al. Applied Catalysis B, V. 73, No. 3-4, p. 311 (2007). ODS is considered a promising substitute or supplement to hydrodesulfurization for deep desulfurization of transportation fuels.
The compositions of common sulfides in fuel oil and their respective sulfones are tabulated in Table 1:
TABLE 1DBT4-Methyl4-Methyl 4,6-Dimethyl4,6-Dimethyl SulfoneDBTDBT SulfoneDBTDBT SulfoneDBT(DBTO2)(4-MDBT) (4-MDBTO2)(4,6-DMDBT) (4,6-DMDBTO2)C H % 82.5870.3683.8172.1684.8873.76S %17.4214.8416.1913.9415.1213.14O %014.80013.90013.10
Sulfones formed by ODS of diesel fuels are complex mixtures that vary based on the crude source and other factors, including DBT sulfone along with several alkyl substituted DBT sulfones, such as 4-MDBT sulfone, 4,6-DMDBT sulfone, 1,4-DMDBT sulfone, 1,3-DMDBT sulfone, TriMDBT sulfone, TriEDBT sulfone, and C3DBT sulfone. The structures of certain sulfones found in ODS treated sulfones are given below.

Unlike hydrodesulfurization, in which desulfurized products remain with fuel oil and organic sulfur is converted into gaseous H2S that leave the product, i.e., fuel oil mixture, sulfones formed by ODS must be separated from the product. Various attempts have been made to dispose oxidized sulfur compounds formed by oxidative desulfurization. These techniques include conventional extraction, distillation and adsorption.
Kocal et al U.S. Patent Publication 2009/0065399 discloses an oxidative desulfurization process in which a thiophene-rich diesel stream is combined with an oxidant to oxidize the thiophenes to sulfones. The resulting stream is separated into sulfone oil and first low-sulfur diesel stream. The sulfone oil is then combined with a caustic stream (e.g., sodium hydroxide, potassium hydroxide, etc.) to produce a second low-sulfur diesel stream and sodium sulfide organic compounds. However, sulfone oil must be extracted first to reduce the volume that needs to be treated with caustic stream. The solvent extraction processes can result in an undesirable loss of hydrocarbon product yield. The mixing of sulfone oil with caustic stream generates a liquid-liquid multiphase system from which the aqueous sulfite solution settles.
With the steady increase in demand for hydrocarbon fuels having an ultra-low sulfur level, a need exists for an efficient and effective process and apparatus for desulfurization while maximizing product yield.
Accordingly, it is an object of the present invention to effectively reducing the concentration of oxidized sulfur compounds from a mixture of liquid hydrocarbons and the oxidized sulfur compounds.